Sep 2026· Journal of the American Chemical Society· Vol 148, pp. 39839-39846· 0 citations· 63 references
Abstract
Intersite electronic coupling underpins cooperative behavior in biological systems and heterogeneous catalysts, yet how such coupling emerges and evolves with oxidation state remains poorly understood. Here, we use atomically precise Fe3Co6Se8L′6 (L′ = PPh2N(−)Tol) clusters to establish a direct connection between redox chemistry and intersite electronic communication within a well-defined metal–chalcogenide framework. Inner-sphere trioxidation of the cluster enables redistribution of charge across the Fe edge sites and the Co6Se8 support, as evidenced by single-crystal X-ray diffraction analysis, 57Fe Mössbauer spectroscopy, and magnetic and electrochemical measurements. The oxidized clusters exhibit a low-energy near-IR charge-transfer band and an overall antiferromagnetic response, while density functional theory reveals Fe/Se/Co orbital mixing and spin density distributed throughout the Fe–Se–Co framework. Together, these results identify a redox-dependent, support-mediated coupling regime in which the Co6Se8 scaffold electronically links spatially separated Fe sites.
Transition-metal incorporation is widely employed to enhance the photoelectrochemical performance of BiVO4 photoanodes, yet how the local incorporation environment governs charge-carrier dynamics remains poorly understood. Here, we establish a structure-function relationship between the local environments of Fe, Co, an...
A. García-Eguizábal, Camilo A. Mesa, Mariam Barawi et al.· Angewandte Chemie· 0 citations
In molecular complexes, ligand-to-metal charge transfer (LMCT) excited states enable efficient photoinduced charge separation and strong redox reactivity, but their operation is typically limited to short ultraviolet excitation. Extending LMCT absorption into the visible region utilizing strongly donating ligands often...
Tian-Na Liu, Wen-Zhe Shang, Wei Che et al.· Angewandte Chemie· 0 citations
Polyoxometalates (POMs) are redox-active metal–oxo clusters of central interest in molecular and materials chemistry. The giant mixed-valence {Mo154} ring, built from 14 repeating subunits, is a prototypical system expected to exhibit rich electronic functionality; however, its transport has often been obscured by wa...
H. Kishimoto, Yuma Kondo, Tomoki Misaka et al.· Journal of Physical Chemistr...· 0 citations
Fully exposed metal cluster catalysts combine the atomic precision of single-atom catalysts with the multi-site reactivity of nanomaterials; however, achieving both structural stability and site-specific bifunctionality remains challenging. Herein, we report a Janus-type bifunctional catalyst comprising fully exposed a...
Ming-Yang Liu, Jiao Li, Qi Li et al.· Angewandte Chemie· 0 citations
Covalent organic frameworks (COFs) are promising photocatalysts for the oxygen reduction reaction (ORR), yet reconciling the different electronic requirements in different elementary steps remains challenging. Herein, guided by the Sabatier principle and Marcus-Hush electron-transfer theory, we report a PyaD COF with d...
Uranium removal from water is crucial, yet conventional photocatalysis is limited by carrier recombination and poor charge transfer. Herein, a dual‐site electronic coupling channel modulation strategy is proposed by tuning metal sites in both the porphyrin center and paddlewheel nodes of two‐dimensional porphyrinic...
Peng-De Li, Hang-Xing Wu, Bin Zuo et al.· Advanced Functional Material...· 0 citations
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